CN105694793B - There is the reactive adhesive of improved adhesiveness to metal surface - Google Patents

There is the reactive adhesive of improved adhesiveness to metal surface Download PDF

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Publication number
CN105694793B
CN105694793B CN201510932369.0A CN201510932369A CN105694793B CN 105694793 B CN105694793 B CN 105694793B CN 201510932369 A CN201510932369 A CN 201510932369A CN 105694793 B CN105694793 B CN 105694793B
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ground
polyurethane
product
weight
adhesive
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CN105694793A (en
Inventor
B·W·卡尔森
R·保罗
M·穆万达米纳
F·D·马伊
D·B·马尔科姆
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HB Fuller Co
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HB Fuller Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00—Floor coverings
    • B32B2471/02—Carpets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/003—Presence of polyurethane in the primer coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

A kind of reactive adhesive to metal surface with improved adhesiveness.The invention discloses a kind of aqueous adhesive compositions, and it includes the solid isocyanate of surface passivation and the blends of two kinds of different polyurethane.Also disclose that the method for preparing the product comprising adhesive coating and prepared product.

Description

There is the reactive adhesive of improved adhesiveness to metal surface
Technical field
The present invention relates to aqueous adhesive compositions.Especially, described adhesive composition includes the solid of surface passivation Isocyanates and two different dispersions of polyurethanes having to the reactive functional group of isocyanates.
Invention content
In one aspect, the present invention relates to a kind of aqueous adhesive compositions, contain：The solid isocyanic acid of surface passivation Ester；The first dispersions of polyurethanes contains with the first polyurethane to the reactive functional group of isocyanates；With Two kinds of dispersions of polyurethanes contain second polyurethane different from the first polyurethane.Second of the polyurethane is carboxylic Sour functional polyurethanes, the acid value with 10-30 and with no more than about 50,000g/mol single mode weight average molecular weight (Mw)。
In one embodiment, the first polyurethane has the not less than about weight average molecular weight of 50,000g/mol (Mw).
On the other hand, the present invention relates to a kind of product, it includes：Ground, and positioned at least one surface of ground On adhesive phase.Described adhesive layer contains：The solid isocyanate of surface passivation has reactive to isocyanates The first polyurethane of functional group, and second polyurethane different from the first polyurethane.Second of the polyurethane is carboxylic Sour functional polyurethanes, the acid value with 10-30 and with no more than about 50,000g/mol single mode weight average molecular weight (Mw)。
On the other hand, the present invention relates to a kind of product, it includes：First ground, the second ground, and it is located at the first bottom Adhesive phase between material and the second ground.Described adhesive layer is derived from the above-mentioned aqueous adhesive compositions of any type 's.
On the other hand, the present invention relates to a kind of methods preparing the product with the first ground.The method includes：It will The above-mentioned aqueous adhesive compositions of any type are applied in the first main surface of the first ground, and the dry aqueous binders Composition in the first main surface of the first ground to form adhesive coating.
In one embodiment, the method further includes that the second ground is made to be contacted with described adhesive layer, so that One ground and the second ground are contacted with positioned at the adhesive phase between them to form product, and are heated and applied to product and press Power.
On the other hand, the present invention relates to a kind of methods preparing the product with the first ground and the second ground.This Method includes：The above-mentioned aqueous adhesive compositions of any type are applied in the first main surface of the first ground with shape on it Composite adhesives coating makes the second ground be contacted with adhesive coating so that the first ground and the second ground and between them Adhesive phase contact to form product, and pressure is heated and applied to product.
In some embodiments, at least one ground is metal substrate.
The aqueous adhesive compositions of the present invention are used for will via the adhesive coating derived from aqueous adhesive compositions Two bond substrates are together.
Adhesive coating can be with any suitable thickness, including for example, at least 10 microns (μm), at least 25 μm, at least 50 μm, about 25-200 μm, or about 25-150 μm.
Adhesive coating can be formed using various technologies, such as include directly coating one in a main surface of ground Layer so that dried adhesive coating multipass applicator (such as additional aqueous adhesive compositions are coated to through dry On dry adhesive coating, coated Aquo-composition (this process can be repeated as many times) is then in addition dried) and they Combining form.Adhesive coating can be derived from identical or different aqueous adhesive compositions.
Drying temperature can be any suitable temperature or set temperature, it is preferred that being maintained at sufficiently low to prevent surface The temperature of the solid isocyanate activation (being crosslinked) of passivation.During drying, adhesive phase is preferably remained in no more than about 70 DEG C, no more than about 60 DEG C or even no greater than about 55 DEG C of temperature.
Adhesive coating on ground can be heated to for example, at least 60 DEG C, at least 75 DEG C, about 60-150 DEG C or about 75-100 DEG C of temperature, to activate the solidification of the layer to form solidification bonding between ground or between two grounds.
The crystallinity and peak melt temperature that adhesive coating preferably has are sufficiently high to allow the fortune of the ground of precoating Defeated and storage, and it is sufficiently low so that adhesive coating is cured thermal activation.It is a kind of weigh crystallinity useful means be molten Change enthalpy.The fusion enthalpy and peak melt temperature of adhesive coating are detected using dry binder film.In the feelings of desciccator diaphragm Under condition, adhesive coating shows that fusion enthalpy is at least 25J/g, about 25-70J/g, or about 35-70J/g.
Adhesive coating is it is also preferred that peak value display melting temperature is at least 30 DEG C, at least 40 DEG C, about 30-80 DEG C, or about 40- 60℃。
The ground with dry adhesive coating of precoating is the stable storing under room temperature (i.e. about 22-25 DEG C), and And it remains heat-setting.
Adhesive coating is shown to be counted relative to reference substance (EM9002-100, commercially available from HB Full (St.Paul, MN)) 180 degree peel strength increase at least 30%, at least 50%, at least 60%, this removes strong according to solidification 180 degree described herein Spend experimental method detection.
Other features and advantages of the present invention will be described by following description and claim below.
Term
Term " polyurethane " indicates polyurethane and the polyurethane containing urea groups in polyurethane backbone.
Term " aqueous dispersion " indicates aqueous dispersion, aqueous emulsion, aqueous suspension and aqueous solution.
Other feature and advantage will be embodied by preferred embodiment and claim below.
Detailed description of the invention
Aqueous adhesive compositions
The present invention aqueous adhesive compositions include：The solid isocyanate of surface passivation contains the first polyurethane The first dispersions of polyurethanes, and second of dispersions of polyurethanes containing second of polyurethane.
The first dispersions of polyurethanes contains the first polyurethane, the first described polyurethane has energy and isocyanate group The functional group of group's reaction.Second of dispersions of polyurethanes is different from the first dispersions of polyurethanes.Second of the poly- ammonia Ester dispersion includes second of polyurethane, is carboxylic-acid functional polyurethane, has other officials reactive to isocyanates It can group.Two kinds of dispersions of polyurethanes and the solid polyisocyanate of surface passivation can respectively be provided as two parts system, so It is blended together before the use afterwards.Alternatively, two kinds of dispersions of polyurethanes and the solid polyisocyanate of surface passivation can conducts A system provides, this system includes the blend of two kinds of dispersions of polyurethanes and the solid isocyanate of surface passivation.
Aqueous adhesive compositions can be applied to using various application techniques in the main surface of ground, including spraying (example As spiral and splash spray), coat (such as roller, slit, heliogravure, curtain coating and pattern) and combination thereof.One kind has Method of application includes being rolled onto Aquo-composition on ground according to required coating weight, then so that is had been coated with contains Water composition passes through from dry channel to form dry adhesive coating.Drying temperature in the channel can be any suitable Temperature or set temperature, it is preferred that being maintained at sufficiently low to prevent the solid isocyanate of surface passivation from activating (be crosslinked) Temperature.During drying, adhesive coating preferably remain in no more than about 70 DEG C, no more than about 60 DEG C or even no greater than about 55 DEG C of temperature.
The first dispersions of polyurethanes
The first dispersions of polyurethanes includes the first polyurethane, the first described polyurethane is film forming, Ke Yishi The blend of single polyurethane or at least two different polyurethane.The first polyurethane includes can be anti-with isocyanate functional group The functional group answered.It is useful to the reactive functional group of isocyanates include hydroxyl, amino, carboxylic acid, amide, thiol group and A combination thereof.
The first polyurethane preferably has not less than 50,000 grams/mol (g/mol) and is not more than 125,000g/mol Or the weight average molecular weight no more than 100,000g/mol.
The first suitable polyurethane is to be derived from polyalcohol and polyisocyanates.The example of useful polyalcohol includes poly- Ester polyol, polyether polyol and combination thereof.Useful polyester polyol includes such as crystalline polyester polyol and nothing Amorphous polyester polyol.
Suitable polyester polyol include for example derived from unbranched dicarboxylic acid, dicarboxylic acids derivative (such as acid anhydrides, ester and Acyl chlorides), the polyester polyol of aliphatic polyol, alicyclic polyol, straight chain polyalcohols, Branched polyol and combinations thereof.It is useful The example of the dicarboxylic acids for being used to form polyester polyol include adipic acid, succinic acid, decanedioic acid, dodecanedioic acid and its group It closes.The example of the useful aliphatic diol for being used to form polyester polyol includes ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, neopentyl glycol and combination thereof.Useful polyester polyol includes for example from 1,4- Polyester polyol derived from butanediol, 1,6- hexylene glycols and combinations thereof, such as including derived from adipic acid and 1,4-butanediol Polyester polyol, from polyester polyol derived from adipic acid and 1,6- hexylene glycols, from adipic acid, 1,6- hexylene glycols and neopentyl glycol Derivative polyester polyol, and combinations thereof.
Suitable polyether polyol includes from cyclic oxide such as ethylene oxide, propylene oxide, epoxy butane and tetrahydrochysene The product that the polymerization of furans obtains, or added to from one or more this oxides with the multifunctional of at least two active hydrogens The product obtained on initial compounds, multifunctional initial compounds are, for example, water, polyalcohol (such as it is ethylene glycol, propylene glycol, two sweet Alcohol, cyclohexanedimethanol, glycerine, trimethylolpropane, pentaerythrite and bisphenol-A), ethylenediamine, propane diamine, triethanolamine, with And 1,2- propanedithiols.Particularly useful polyether polyol includes such as polyoxypropylene diols and triol, passes through ethylene oxide Poly- (oxypropylene-oxyethylene) glycol and triol obtained in suitable starter is simultaneously or sequentially added to propylene oxide, And the polytetramethylene ether diol obtained by tetrahydrofuran by polymerization.
The first useful polyurethane has at least two free isocyanate groups groups in per molecule, including such as two is different Cyanate, triisocyanate, more advanced polyisocyanates and combinations thereof.The example of useful polyisocyanates includes such as fat (cyclo) aliphatic diisocyanates (such as hexamethylene diisocyanate (HDI), tetramethyl xylylene diisocyanate (TMXDI)), fat Ring race isocyanates (such as 1- isocyanate groups -3,3,5- trimethyls -5- isocyanatometyls-hexamethylene (IPDI) hydrogenate methylene Base diphenyl diisocyanate (H12MDI)), (such as methylenediphenyl two is different for heterocyclic isocyanate and aromatic isocyanate Cyanate (MDI), toluene di-isocyanate(TDI) (TDI), naphthalene -1,5- diisocyanate (NDI), 3,3 '-dimethyl diphenyl -4, 4 '-diisocyanate (TODI), the urea diketone (MDIU) of dimerization MDI, MDI, the urea diketone (TDIU) of TDI, 3,3 '-diisocyanates Ester -4,4 '-dimethyl-n,N'-diphenylurea (TDIH), 2 moles of 1- methyl -2,4- phenylene vulcabonds and 1 mole 1, The addition compound product of 2- ethylene glycol or 1,4- butanediols；The addition compound product of 2 moles of MDI and 1 mole percent；And their group It closes.
The first useful dispersions of polyurethanes is preferably anionic property dispersions of polyurethanes.The first useful commercially available The example of dispersions of polyurethanes includes DISPERCOLL U53, DISPERCOLL U56, DISPERCOLL U XP 2682, DISPERCOLL U 8755,DISPERCOLL U 2815 XP,DISPERCOLL U54,DISPERCOLL U XP 2710, DISPERCOLL U 2849 XP, DISPERCOLL U42 and DISPERCOLL U XP 2643, they can be from Bayer Material Science AG (Germany) are obtained；With LUPHEN 585, LUPHEN 3615, LUPHEN D 207E and LUPHEN D DS 3548, they can be obtained from German BASF.
Second of dispersions of polyurethanes
Second of dispersions of polyurethanes includes second polyurethane different from the first above-mentioned polyurethane.Second of poly- ammonia Ester is carboxylic-acid functional polyurethane, the acid value with 10-30 or 15-25mg/gKOH.
Second of polyurethane preferably has lower weight average molecular weight (Mw).It is not more than it is preferred that second of polyurethane has The single mode weight average molecular weight of 50,000g/mol.
Second of polyurethane is film forming, can be single carboxylic-acid functional polyurethane or at least two different carboxylics The blend of sour functional polyurethanes.
Second of polyurethane can include the additional functional group that can be reacted with isocyanate functional group.It is useful to isocyanic acid The reactive functional group of ester includes such as hydroxyl, amino, amide, thiol group and combinations thereof.
The example of useful commercial polyurethane dispersion includes DISPERCOLL U2824 XP, can be from Bayer Material Science AG (Germany) are obtained.
The presence of the first polyurethane and second of polyurethane to glue derived from aqueous adhesive compositions of the present invention Mixture coating includes at least 30 weight %, at least 50 weight %, at least 70 weight %, at least 80 weight %, about 30-97 weight Measure %, about 50-95 weight %, the first polyurethane of about 70-95 weight % or about 80-95 weight % and second polyurethane Mixture, the weight meter based on dry adhesive coating.
The amount of second of polyurethane is at least 10 weight %, at least 20 weight %, about 10-60 weight %, about 20-50 Second of the polyurethane of weight %, the weight meter of the mixture based on the first polyurethane and second of polyurethane.
The solid isocyanate of surface passivation
The solid isocyanate of surface passivation is the form of solid particle, and is used as crosslinking agent.Useful surface passivation Solid isocyanate can be derived from polyisocyanates and passivator.
Various polyisocyanates are suitable, including for example aliphatic, alicyclic, heterocycle and aromatics isocyanates.It is useful The specific example of polyisocyanates include dimerization 4,4'-MDI, the urea diketone (MDIU) of MDI, the urea diketone (TDIU) of TDI, 3, 3'- diisocyanate -4,4'- dimethyl-N, N'- diphenyl ureas (TDIH), 2 moles of 1- methyl -2,4- phenylene diisocyanates The addition compound product of ester and 1 mole of 1,2- ethylene glycol or 1,4-butanediol, the addition compound product of 2 moles of MDI and 1 mole percent are different The isocyanuric acid ester (IPDI-T) and combination thereof of isophorone diisocyanate.
Can include the urea diketone of TDI by the commercially available solid isocyanate of surface passivation (for example, can be from Rhein Chemie The ADOLINK TT that Rheinau GmBH (Mannheim, Germany) are obtained, can obtain from Danquinsa GmBH (Germany) DANCURE 999, THANECURE T9 (TSE, Clearwater, Florida))；DESMODUR LP BUEJ 471, are super Miniaturization IPDI- isocyanuric acid esters can be obtained from Bayer Material Science AG (Germany)；And the urea diketone of MDI (GRILBOND A2BOND can be obtained from EMS-Griltech (Switzerland)).
The solid isocyanate of surface passivation is preferably passivated in the presence of passivator.Useful passivator includes such as fat Race's primary amine, aliphatic secondary amine, diamines, polyamines, hydrazine derivate, amidine, guanidine, and combinations thereof.The example of useful passivator includes second two Amine, 1,3- propane diamine, diethylenetriamines, trien, 2,5- lupetazins, 3,3'- dimethyl -4,4'- diaminos Base-dicyclohexyl methyl hydride, methyl nonamethylene diamine, isophorone diamine, 4,4'- diamino-dicyclohexyl methanes, diamino polypropylene Ether, triamido polypropylene ether, polyamidoamines amine, the passivator disclosed in 6,348,548 B1 of US, and combinations thereof.
The solid isocyanate of surface passivation can be prepared according to various methods, including for example in 6,348,548 B1 of US Described in method, its content is incorporated herein by reference.
The solid isocyanate of surface passivation can be various forms, including such as aqueous suspension, micronization particle, And combinations thereof.
The commercially available solid isocyanate of useful surface passivation includes that (surface is blunt by such as DISPERCOLL BL XP 2514 The water slurry of the isocyanates of change contains the urea diketone of about 40% TDI), it can be from Bayer Material Science AG (Germany) is obtained), and can be from the Aqualink U of Aquaspersions Limited (UK) acquisitions.
The solid isocyanate of surface passivation can be blended with dispersions of polyurethanes to form stable Aquo-composition.
Aquo-composition preferably comprises at least 0.25 weight %, at least 0.5 weight %, at least 1 weight %, about 0.25-10 Weight %, about 0.5-8 weight % or the isocyanates of the even surface passivation of about 1-5 weight %, the weight based on Aquo-composition Gauge.
Additional component
Aquo-composition optionally includes various other additives, including for example other polymer, catalyst (such as based on Amine), preservative, pH modifiers (such as ammonium hydroxide), adhesion promotor (such as compound of silane-containing), tackifier (such as grind Grind tackifier), pigment, surfactant, foam inhibitor, antifoaming agent, antifungal agent, antibacterial agent, thickener, end-capping reagent and stabilization Agent (such as amine), filler (such as carbonate, talcum, starch), helping binder film to form the material of barrier, (such as nanometer is viscous Soil), insulating materials (such as inorganic filler, glass microbubbles), rheology modifier, salt and abrasive flour, conductive material (such as Various metals (such as silver)), and combinations thereof.
Other suitable polymer (being known as may include the third polymer in Aquo-composition) include for example to different The polyurethane of cyanate functional group anergy；Vinyl copolymer (VAE)；To isocyanate functional group without anti- The polyacrylate of answering property；Polyacrylonitrile (such as hycar)；Styrene butadiene ribber (SBR)；And its Combination.
When the third polymer is present in adhesive coating, the first polyurethane, second of polyurethane, surface passivation Solid isocyanate and the total amount of the third polymer reach at least 90 weight %, at least 95 weight % or even at least 98 weights Measure %, the weight meter based on dry adhesive coating.
One example of useful stabilizer is JEFFAMINE T-403 POLYETHERAMINE, can be from Huntsman Corporation (The Woodlands, Texas) is obtained.
Useful thickener includes that can for example be obtained from OMG Borchers GmbH (Langenfeld, Germany)GEL A LA, and can be obtained from BASF Chemical Company (Ludwigshafen, Germany) STEROCOLL HT。
One example of useful preservative is the ACTICIDE MBS that can be obtained from Thor GmbH (Speyer, Germany).
Product
Aqueous adhesive compositions can be used for producing the product for including at least one ground, or include the first ground and the The product of two grounds.
In one embodiment, product includes at least one ground and the adhesive in a main surface of ground Layer.Adhesive phase includes the solid isocyanate of surface passivation, with the first to the reactive functional group of isocyanates Polyurethane, and second polyurethane different from the first polyurethane.Second of the polyurethane is carboxylic-acid functional polyurethane, Its acid value with 10-30 and with no more than about 50,000g/mol single mode weight average molecular weight (Mw).
Ground can be metal substrate or non-metal substrate.
In another embodiment, product includes the first ground, the second ground, and between the two grounds simultaneously The adhesive phase derived from any aforementioned present invention aqueous adhesive compositions being in direct contact with the two grounds.First bottom One in material and the second ground is metal substrate.Another in first ground and the second ground can be identical or different Ground, and if it's different, it can be selected from any " nonmetallic " ground as described herein, or be selected from different types of metal Ground.
The example of metal substrate include aluminium, steel, copper, metallic composite, metal foil, metal film, metalized surface and its Combination.
The example of non-metal substrate includes various textiles (such as fabric (such as the microfibre based on polyethylene, cotton, sail Cloth and non-woven fabric), dermatine and fur, foil (such as decoration foil), paper, film (such as plastic foil (such as polyester, polyamides are sub- Amine (i.e. Kapton), polypropylene and polyethylene)), and combinations thereof.
The example of other non-metal substrates includes tile, ceramics, (such as polyamide (such as nylon), polyurethane gather plastics Carbonic ester, acrylonitrile-butadiene-styrene copolymer (ABS), ABS/ polycarbonate Alloys, polyether-ether-ketone (PEEK) etc.), Plastic composites (such as fibre-reinforced plastics), glass, cardboard, timber and the product containing timber.
First ground and the second ground can be identical or different materials, but in the first ground and the second ground extremely Few one is metal substrate.
These grounds can be the form of single-layer or multi-layer.
Ground may be pretreated to improve the bonding between binder film and ground.Useful pretreatment includes for example Sided corona treatment, plasma treatment, flame treatment, chemical primers and combinations thereof.
The product of the present invention can be prepared by various methods, and include the main surface that Aquo-composition is deposited to ground On, and by Aquo-composition than being cured work between the blend of two kinds of polyurethane and the solid isocyanate of surface passivation It is dry at the lower temperature of temperature of change, to form the preparation of coating.The coated ground of gained is to store at room temperature Stable, and can use later.
In one embodiment, the product with the first ground is prepared by the following method：It will be in any type Aqueous adhesive compositions are stated to be applied in a main surface of the first ground, and the dry adhesive composition being applied with Adhesive coating is formed in first main surface of the first ground, to form the product (or ground) of precoating, can be stored And transport different positions.After the completion, the product of precoating can be used for producing final product as follows：Make the second ground with Adhesive coating contacts so that the first and second grounds and the adhesive coating between the two grounds are in direct contact with shape At product, and pressure is heated and applied to this product, to allow the adhesive coating solidification of coating so that the two grounds pass through It is bonded together by adhesive phase.
In another embodiment, the product with the first ground and the second ground is prepared by the following method： The above-mentioned aqueous adhesive compositions of any type are applied in a main surface of the first ground, and make the second ground and bonding Agent coating layer touch is so that the first and second grounds and the adhesive coating between the two grounds are in direct contact to form system Product, and this product is heated and applies pressure to allow adhesive coating to cure, so that the two bond substrates are together.
In one embodiment, the main surface of each first ground and the second ground can be used before being in contact with each other and appoint A kind of what above-mentioned aqueous adhesive compositions precoating.
The product can be heated to the temperature that can be activated isocyanates and start solidification process.In some embodiments In, the product can be heated to for example, at least 60 DEG C, at least 75 DEG C, about 60-150 DEG C or about 75-100 DEG C of temperature with work The solidification for changing thermosetting adhesive layer, it is viscous to form the solidification bonding between ground or the solidification between two grounds It closes.Pressure can be used for helping forming bonding (such as film or tyre press, heated platen).
Using
Aqueous adhesive compositions can be used for producing various products, including such as automobile component, railway carriage shell, tissue layer Laminate, various assembled articles, underlayment bottom and electronic product.
The present invention is described below by embodiment.Unless otherwise indicated, all ratios and percentage are all according to weight meter.
Embodiment
Experimental procedure
Unless otherwise indicated, the experimental procedure used in embodiment and specification includes following process.
Molecular weight
Gel permeation chromatography (GPC) molecular weight distribution curve of each polyurethane samples is detached using Waters 2695 What module (Separations Module) obtained, it connect with 2414 refraction indexs of Waters (RI) detector, is rubbed with 0.05 That (M) lithium bromide/dimethylformamide (LiBr/DMF) mobile phase is via Agilent Resipore GPC column operations.Divide equally again Son amount (Mw) data are relative to polymethyl methacrylate criterion calculation.
Peak melt temperature and fusion enthalpy detection method
The peak melt temperature and fusion enthalpy (Δ H) of dry thermosetting adhesive film are used after removing thermal history What 1 differential scanning calorimeter (DSC) of Perkin Elmer, Pyris detected under 10 DEG C/min of the rate of heat addition.
Acid value
Acid value is " to be used for the standard test method of urethane raw according to entitled：Detect the acid value and base number of polyalcohol " ASTM D 4662 detect, unlike using isopropanol replace ethyl alcohol.
Cure 180 degree peel strength detection method
Detection solidification 180 degree (180 °) peel strength is to use Instron detector model 5500R (- Instron Corporation, Norwood, MA) according to it is entitled " for bond properties divest or the standard test method of peel strength " ASTM D903-98 experimental methods detection, difference is as follows：
1. the speed of experiment of machine driving handle/track rate：Instead of 305mm/min, the speed of 300mm/min is used for sample Product examine is surveyed.
2. testing the length of ground and bonding：
- 7 inches of (in) (177.8mm) flexible substrates are for detecting, instead of 12in (304.8mm) flexible substrates,
- 3in (76.2mm) hard ground is for detecting, instead of 8in (203.2mm) hard ground,
The bond length of -2.5in (63.5mm) inch is for detecting, instead of the bond length of 6in (152.4mm)；With
3. sample is adjusted 24 hours under 25 DEG C +/- 1 DEG C and the relative humidity of 50%+/- 2%.
Report the mean peel strength value for 6 samples, unit is N/25mm.
Preparation of samples for curing the experiment of 180 degree peel strength
By hard stainless steel (SS) ground sample (grade of 1in x 3in x 0.040in (25.4mm x 76.2mm x 1mm) Other 304, come from Q-Lab, Westlake, OH) use isopropanol (IPA) wiping and drying.By 1in x 2.5in x 0.004in The adhesive films samples of (25.4mm x 63.5mm x 0.1mm) are removed from isolation liner bottom to be placed on SS grounds.Then by 1in X 7in (25.4mm x 177.8mm) flexible nylon ground is placed in the top of SS/ binder film laminate structures.Nylon fabric is NYLON SUPPLEX (Invista, Wichita, KS) have 117.4g/m2The blue Changchun loom figured (Blue of weight Periwinkle Fabric) or equivalent.Then use heated platen machine by SS/ binder films/nylon fabric laminate structures It is bonded together at the cured temperature for being enough to activate adhesive phase.By this structure using heated platen machine in the following conditions Under be bonded together：
Bond line temperature:90℃
Pressure:22N/cm2(on sample)；With
Time in the case where bonding line temperature:60 seconds.
The example of suitable heated platen machine is Sonitek Spectrum Heat Sealer, model SB-3 4.2, can It is obtained from Sonitek (Milford, CT).
Embodiment
According to acid value described herein and molecular weight detection method, the acid value and again of each commercial polyurethane dispersion is detected Average molecular weight.As a result it is listed in Table 1.
Table 1
Embodiment 1-3 and comparative example 1-3
Each sample of Reference Example, comparative example 1-3 and embodiment 1-3 is to be derived from each aqueous combination as shown in Table 2 Object, and prepared according to about the preparation of samples method described in solidification 180 degree peel strength detection method, media thickness It is 100 μm +/- 10 μm.
Then sample is detected according to various detection methods as described herein.As a result it is also listed in Table 2.
Table 2
* EM9002-100 can be obtained from HB Fuller (St.Paul, MN)
Other embodiments are within the scope of the claims.All publications incorporated herein are incorporated herein for ginseng It examines.

Claims (11)

1. a kind of aqueous adhesive compositions, contain：
The solid isocyanate of surface passivation,
The first dispersions of polyurethanes contains with the first polyurethane to the reactive functional group of isocyanates, and
Second of dispersions of polyurethanes contains second polyurethane different from the first polyurethane, second of the poly- ammonia Ester is carboxylic-acid functional polyurethane, the acid value with 10-30 and with the single mode Weight-average molecular no more than 50,000g/mol It measures (Mw).
2. the aqueous adhesive compositions of claim 1, wherein the first polyurethane are with not less than 50,000g/mol and less In the weight average molecular weight (Mw) of 125,000g/mol.
3. the amount of the aqueous adhesive compositions of claim 1, the wherein solid isocyanate of surface passivation is 0.25-10 Weight %, the weight meter based on composition.
4. a kind of product, it includes：
Ground, and
Adhesive phase at least one main surface of ground, solid isocyanic acid of the described adhesive layer containing surface passivation Ester has the first polyurethane to the reactive functional group of isocyanates, and different from the first polyurethane second Kind of polyurethane, second of the polyurethane are carboxylic-acid functional polyurethane, the acid value with 10-30 and with no more than 50, The single mode weight average molecular weight (Mw) of 000g/mol.
5. the product of claim 4, wherein ground are metal substrate or non-metal substrate.
6. a kind of product, it includes：
First ground,
Second ground, and
The adhesive phase derived from the aqueous adhesive compositions of claim 1, between the first ground and the second ground.
7. the product of claim 6, wherein one in the first ground and the second ground is metal substrate.
8. a kind of method preparing product, the method include：
The aqueous adhesive compositions of claim 1 are applied in the first main surface of the first ground, and
The dry aqueous adhesive compositions in the first main surface of the first ground to form adhesive coating.
9. the method for claim 8 further includes that the second ground is made to be contacted with described adhesive layer, so that the first ground and It two grounds and is in direct contact positioned at the adhesive phase between them to form product, and
Pressure is heated and applied to product.
10. the method for claim 9, wherein one in the first ground and the second ground is metal substrate.
11. the method for claim 9, wherein the second ground before being contacted with the adhesive coating on the first ground With derived from the aqueous adhesive compositions of claim 1 adhesive phase coat in advance.
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